Gas generation



GAS GENERATION Percival C. Keith, Peapack,`N. J. Continuation of application Serial No. 692,875, August 24, .1946. This application August-5, 1952, SerialNo. 302,771

3 Claims. (Cl. 18-196) The present invention relatesttothe generation of gases and is more specificall-y concerned `:with the generation .of essentially hydrogen-:carbonmonoxide rmixtures of `.the type known as synthesis gas suitable for use in the cata- .lytic manufacture of hydrocarbons and their oxygenated derivatives.

The usual process `for generating mixtures ofhydrogen .and carbon monoxide, hereinafter referred to 'forpun poses of .convenience as "synthesis gasjhfrom hydrocarbons involves essentially the reaction of hydrocarbons i `sion.

` This normally means that thegaseous product is discharged. from the generator at ahigh temperature. For example, 'in many operations of whchl `am aware the synthesis gas frequently flows out of the generator `at a temperature of 2100 F., andsometimes as high as 3000 F. or thereabove. Temperatures of this range and even substantially therebelow introduce ,major problems ofconstruction and engineering since they are far above the range in which tgases can be `handled byconventional tubing and equipment. The same remarksapply to the useot conventional heat.exchangers which become a practical necessity where the :process is to be operated under the usual limitations oft-good heat conservation.

One object of the presenttinvention is to provide for the prompt cooling of` the synthesis gastfrom thetrgenerator under conditions which `result in a sharp ;temperature drop to a condition wherein thegasestare capable of being readily handled and particularly wherein .the energy change involved intthis temperature .drop. may ,be `eciently converted tousefu1 purposes. Inthisconnection an important object contemplates the` rapid cooling of the gases undertsuchconditionsthat the cooling instrumentalities may operate under .reasonablerandrpractical ranges of temperature and Inayaccordingly` beconstructed of conventional materials to` generate steam or otherwise usefully employtthe availablettthermalenergy at reasonable temperatures.

Another important object of :the pres ent invention contemplates the process of gas generation undertsubstantia11y uniform conditions of temperature, time ,of contact,

and admixture of the `:reactartsin a generation .zone of `tpredeterrnined size and .character:particular1y wherein the products are sharply` reducedin temperature in order to terminate reaction immediately at the extremity of thegas generation Zone.

:Other important ,objects contemplate the controlled interaction of the reactants, together with rapid and con- 'trolled quenching of the products, and the provision of asystem wherein a contact mass orpowdered thei-mophore operates in the cooling or quenchng zone.

The invention more particularly contemplates thegennited States Parent 2,779367 ?atentati Jan. :2 9, 1957 eration of synthesis gas at elevated temperaturs with discharge of the product, `at ;high 'temperatures and as formed, directly into a fiuidizedmass-of solid `paflcles disposed in heat exchange relation to adequate cooling surfaces operative tomaintain -thefluidizedmass ;at uni- .forrn temperature quite materially below that-of the gas generation zone. The flow of gas from the `geierator may `be` quite a adequate totmaintain the i powdered thermophore or contact mass in a state of proper fluidization whereby the rate of heat transfer to the cool surfaces is materially enhanced and the entire cooling .zone `maintained continuously at a relativelylow temperature,` free from the detrimental effects ofexcessive thermal .conditons.

As is known, thegtechnique ,of ;fluidizationnormally involves the passage of a gas upwardly through amass of solid `particles of such `size, relative :to ;the rate of gaseousflow, thatthe particles are individually Suspended in 'the ,gas and yet exhibit "hindered settling" ozslippage in the gas stream. 'When such a system isoperated under a condition kno wntastdense phasefluidization, the powder assumes the appearance of .a boilingr liquid with awal]- de'fined upper pseudo liquidsurface or-leveliromwhich the gaseous products .emerge.

Fludization results in a ,number of advantages, most important of which are a propensity .toward complete `uniforniity of temperature and other tconditionstthroughout the mass of particls and themaintenance ojfan `exceptionally good degree of heat transfer between the ,several phases of the .system and the cooling surfaces,

usually characteristic of exceptionally good liquid ;heat transfer. `Presumably these effects are largely or entirely due to the fact that each of the particlessuspended or `buoyed up in the gas flow, tends to vibrate or move i a number of functions depending upon its character and composition. It may be a completely inert material functioning solely as a means for eecting the thermal or other physical results 'desired. In any event it is necessarily formed of some suitable material capable of 'withstanding the temperature andt reaction conditions prevailing in the system. Such a material ,may well be illustrated by any of the common ret'ractories such, 'for example, as magnesa, zirconia, thoria, high-temperature fire clay, Carborundum, graphite and the like.

'Referring now to the accompanying drawing, which llustrates more or less diagrammatically one preferred means for carrying out the process of the present invention, the numeral lil represents agenerator shell of cylindrical cross section closed at its upper and` lower eX- tremity by means of curved wall sections 11 andlZ-respectively. Internally the generator shell' is 'divided into two sections, namely, a lower or-gasgeneration section and an upper, cooling or quenching section.

The gas generation section'consists essentially of-an internal chamber having refractory walls consisting of a central cylindrical section 13, a lower frusto-conical sections 14 and an upper arch 16. The several-sections of the refractory lining are supported in a surrounding 'mass of ref-actory insulating material 17 enclosed bythe with a refractory lining 19 in the form of a cylindrical tube extending into the generation zone and meeting the lower refractory wall 14.

The present llustrative embodiment contemplates the introduction of reactants, such as methane and oxygen with or without additional reactants in admixture through inlet 18. The reactants may advantageously be preheated, either in admixture or separately, by any suitable preheating means, not disclosed, so that they reach the reaction zone in a suitable condition for the production of an essentially hydrogen-carbon monoxide product.

The upper Wall 16 of the gas generation chamber is flared upwardly as at 21 to provide an outlet nozzle or duct which merges at its upper extremity with the frustoconical wall 22 forming the bottom of the quenching or cooling zone. In order to prevent powdered material, as will hereinafter be more fully described, from passing downwardly into the gas generation chamber, the outlet 21 is advantageously provided with a tubular insert 23 extending somewhat thereabove and being surmounted by a vertically spaced baflle 24 of downwardly facing concave arrangement with an annular margin which extends about the upper margin of the tube 23 in spaced 'elation. Obviously, therefore, the gases leaving the reaction zone are free to pass upwardly through the outlet 21 and tube 23 and are directed downwardly and about the margin of the baffie 24 into the powdered fluidized mass 25 occupying the cooling zone.

The cooling Zone is occupied by cooling means which may take the form of any conventional heat exchange element and in the embodimert shown is represented, more or less diagrammatically, by a pair of vertically spaced headers 26 and 27 communicating with a multiplicity of parallel spaced cooling tubes 28. Liquid coolant, such as water, Dowtherm or the like, may be introduced through inlet pipe 29 and circulated out through outlet pipe 30. Alternatively, as is known, the coolant may be caused to vaporize within the cooling unit at any predetermined temperature controlled advantageously by the pressure maintained therewithin, as a means of transforming the available heat energy into a suitable vapor which may be withdrawn by outlet pipe 30. In any event it Will be apparent that the heat thus extracted from the system is ideally in form suitable for further use or recovery.

It is quite desirable that the cooling unit be so constructed and arranged that it not only provides adequate cooling capacity for the flow of hot gases contemplated, but that the cooling surfaces or exchanger be so configurated as to permit relative streamlined flow of the V gases and the fluidized powder thereabout, With complete freedom from so-called dead spots and other areas of localized temperature variation.

The gases which pass into the lower portion of the i cooling zone about the margin of the bafile 24, move upwardly through the fluidized powder, and are liberated from the upper pseudo-liquid level of the powdered mass,

V whence they pass through the filter 31 and outwardly through the outlet conduit 32 for further use or treatment.

In the embodiment disclosed a standpipe means 35 communicating with the interior of the cooling chamber is provided with a suitable mechanical controller or valve 36 such, for instance, as a star feeder, for withdrawing the powder in controlled amounts for treatment. To this end the mechanical feeder 36 discharges into standpipe 37 communicating with a treating vessel 38. An outlet standpipe 39 commnnicates with a second valve 40 which discharges the treated powder.

An inlet pipe 41 permits the introduction of any suitable gaseous stream into the mass of powder in the standpipe 39 and the treating Vessel 38, which passing through the powder under fluidizing conditions, discharges through the filter 42 and the outlet pipe 43. This i .aftords suitable means for lirnting the accumulation of .4 carbon on the powder. In other words, a relatively small stream of oxygen or air supplied through inlet pipe 41 will burn the carbon deposted and permit the return of clean powder to the system.

In operation it will be apparent that the mixture of feed gases is introduced into the reaction zone at such rate and under temperature conditions such as to permit the interaction of the Components. It will be understood, however, that the reaction zone will initially be preheated to the required temperature in any suitable manner, as by burning methane with an excess of oxygen, until the desired temperature is reached. In any event, during settled operation, the interior of the generation zone is held at the appropriate predetermined temperature of reaction. Depending upon the rate of introduction and the relative size of the unit, the reactants may be exposed for a predetermined time period to predetermined uniform conditions of reaction.

Upon discharge from the gas generation zone the gases immediately pass upwardly through the tube 23 about the bafile 24 and into the quenching or cooling zone thereabove.

It is particularly important to note that the cooling zone by virtue of the good conditions of heat transfer and temperature uniformity inherent in the fluidized powder therein may operate at a temperature quite substantially below the temperature of the gases issuing from the generation zone. This temperature, of course, will depend upon size and design of the cooling zone as well as the Construction of the cooling surfaces and the coolant employed in connection therewith. Advantageously, the fiuidized powder in the cooling or quenching zone may be held at a temperature in the range, for example, of 500 F. to 1000 F. and this may be accomplished without excessive size or Complexity of the apparatus. Of even greater importance, however, is the fact that the issuing generator gases need not pass through the usual cooling gradient of substantial extent, but actually are cooled with great rapidity comparable to a quenching action. In effect, and by way of theoretical explanation, it appears that the turbulence of the fluidized mass is such as to continuously present relatively cool particles to the incoming hot stream. In short, there is a temperature drop to the desired level by "dry quenching with relatively cold powder. As a result, no parts of the cooling zone need be subjected to excessive heat and accordingly may operate continuously without the disadvantage of severe thermal conditions.

As before indicated, the cooled synthesis gas passes outwardly through Conduit 32 for further treatment or utilization. In fact, with the present arrangement, the generator gases need not be cooled -or quenched to any temperature lower than that desirable for convenient handling and may pass directly from the conduit 32 into any suitable heat exchanger, steam boilers, or heat engine adapted to economically utilize the sensible heat of the gases. In short, the cooling zone of the present genera'tor may be operated either to re-cover all of the required sensible heat or alternatively may be operated to lower the gas temperature to a resonable range for permitting the efficient use of subsequent heat economizers.

Further utilization of the 'gas forms no part of the present invention but, for purposes of the illustration, this product may be directly supplied, at any appropriate temperature, to the inlet Conduit of a reactor Operating for the catalytic reduction of carbon monoxide by hydrogen in the production of hydrocarbons and/or oxygenated hydrocarbons.

In the treating vessel 38 and the standpipe 39, 'the powder may be subjected to the passage of any suitable treating fluid through line 41. For example, carbon may, and frequently does, -tend to deposit upon the solid particles and this may be burned by the supply of relatively pure oxygen or of an oxygen-containing gas through pipe 41 preferably introduced -at such rate as to maintain 'the powder in a fluidized condition. The gaseous products of com'oustion are withdrawn through pipe 43 and clean powder is returned to the quenching zone. The invention, 'howeven is not limited to the treatment of the powder by burning of the carbon.

The present invention accordingly provides a construction Whereby reactant gases reside for predetermined period of time in good admixture under carefully controlled reaction conditions, are then promptly -cooled to any predetermined temperature, preferably -below reaction temperature, with simple recovery of sensible heat energy and are liherated in ideal condition for further use of treatment.

The invention can best 'be practiced with feed gases comprising, for instance, methane and relatively pure oxygen. On the other hand, it is possible -to include quite substantial proportions of endothermically reacting feeds, namely, carbon dioxide and/ or water vapor.

Where the temperature of the powder withdrawn through the standpipe 35 is too low for the removal of carbon by combustion, it will be appreciated that the trea'ting vessel 38 and standpipe 39 may be operated at a higher temperature by introducing a suitable fuel, e. g., gas oil or methane, through inlet pipe 44. Vessel 33 may also be fired externally, if required.

In accordance with one example, a mixture of methane and oxygen is introduced through inlet 18 in approximately the molar ratio of 2:1, appropriate to permit reaction in the generation zone. The generation zone is maintained at a temperature of about 2100 F. The flow of gas is adjusted to provide an internal linear velocty of about one foot per second in the generator, calculated 'at the approximate temperature of the generator. The rnixture of gas is preheated to about 600 F. The efluent gases pass into the quenching or cooling Zone maintainedcontinuously at a 'temperature of approximately 650 F. throughout and Operating with a mass of fluidized powdered zirconia of from about 200 to 400 mesh.

The residence time of the gas-es in the generator is about 05 second and the residence 'time in the cooling zone is about 1 second. The efliuent gases from the cooling zone consist essentially of hydrogen and carbon monoxide in approximate molar ratio of 2:1 with less than 5% ntrogen, carbon dioxide, and other diluent gases.

The heat recovery from the cooling exchanger in the quenching zone is closely equivalent to 100% of the hoat energy lost through the temperature drop in the generator gases.

In other examples, a portion of the oxygen may be substituted by carbon dioxide and/or water vapor with good conversion substantially in accordance with theoretical.

The term powder' and mass of particles" and the like as used herein are intended to cover 'those compositions of loose, discrete particul-ate material capable of being fluidized in accordance with principles known in the art by the passage of gases vertically therethrough. Such may vary widely in density and particle size and it will be understood that an appropriate flow of gases will be provided to maintain the specified conditions.

The oxygen used in the process of this invention is preferahly of at least 95% purty; such a product is readily available from conventional processes for 'the liquefaction and rectification of air. However, where inert diluents like nitrogen are not considered troublesome in subsequent operations with the synthesis gas produced, air or oxygenenriched air (e. g., 40% oxygen) may `be `utilized.

The present invention -accordingly provides a fast quench for the hot generator gases and permits the effective generation of steam down to, for example, *a gas temperature of S0O F. In addition, it is possible to more accurately control the tine the reactant-s are subjected to controlled reaction conditions. Again, this latter advantage is strengthened 'by `the immediate quenching action without contamination of extraneous liquds which promptly terminates addtional or side reactions or the excessive fermation of carbon which may tend to proceed where high temperatures are unduly prolonged. In addi- 'tion to the advantage of burning the carbon or otherwise treating the solid particles, it is particularly important to note that the invention permits substitution for the gaseous hydrocarbon feed, at least in part, of a hydrocarbon liquid, such as fuel oil, which may be preheated to a vapor state or may actually be sprayed into the as generation zone Where vaporization and combustion immediately proceed.

This application is a con'tinuation of my pending application Serial No. 692,875, filed August 24, 1946, and now abandoned.

Obviously, many modifications and. variations of the invention will be apparen't to those sk-illed in the art in the light of the foregoing disclosures Without any enlargement of the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the following claims.

I claim:

1. In the process for the production of carbon monoxide and hydrogen by reacting hydrocarbon with an oxygen-containing gas at a temperature autogenously maintained in the range of about 2100 to 3000 F. such that said hydrocarbon and oxygen are converted predomi- -nantly to carbon monoxide and lydrogen with the incidental production of free carbon, the improvement which comprises cooling the reaction gases from said reaction temperature to a temperature of about 650 F. in a period of about l second by Contacting said reaction gases with a fluidized dense phase mass of solid particles of refractory maintained at a temperature of 'about 650 F. by direct contact with cooling surfaces, eectng simultaneous cooling of said reac tion gases and removal of free carbon therefrom, withdrawing the thus cooled reaction gases substantially free of carbon from said fluidized mass, withdrawing solid particles of refractory containing entrapped carbon from said fluidized mass, subjecting said withdrawn particles to regeneration by combustion of carbon therefrom with an oxygen-containing gas, and returning regenerated particles to said fluidized mass.

2. In a process for the production of carbon monoxide and hydrogen by reacting 'a hydrocarbon with oxygencontaining gas at a temperature autogenously maintained in the range of about 2100 to 3000 F. efiecting conversion of said hydrocarbon predominantlyto carbon monoxide and hydrogen with the incidental production of free carbon, the improvement which comprises conducting the resulting products of reaction at substantially reaction temperature into a fluidized dense phase mass of solid particles of refractory maintained at a temperature in the range of 500 to 1000 F. elfecting rapid cooling of said reaction products with simultaneous deposition of free carbon in said fluidized mass, discharging cooled gaseous products of reacton substantially free of carbon from said fluidized mass, withdrawing solid particles of refractory containing entrapped carbon from said fluidized mass, and introducing refractory particles substantially free from carbon to said fluidized mass to replace said particles withdrawn therefrom.

3. A process according to claim 2 wheren solid partcles of refractory containing entrapped carbon withdrawn from said mass are subjected to regeneraton by combuston of carbon therefrom with an oxygen-conta'ning gas and refractory particles so regenerated returned to said fluidized mass to replace said withdrawn particles.

References Cited in the file of 'this patent UNITED STATES PATENTS 1,843,063 Burke Jan. 26, 1932 2,051,363 Beekley Aug. 18, 1936 2,396,709 Letter Mar. 19, 1946 2,420,542 Jahnig May 13, 1947 2,443,2l0 Uphan June 15, 1948 2,605,174 jKrejci July 29, 1952 

2. IN A PROCESS FOR THE PRODUCTION OF CARBON MONOXIDE AND HYDROGEN BY A REACTING A HYDROCARBON WITH OXYGENCONTAINING GAS AT A TEMPERATURE AUTOGENOUSLY MAINTAINED IN THE RANGE OF ABOUT 2100 TO 3000*F. EFFECTING CONVERSION OF SAID HYDROCARBONS PREDOMINANTLY TO CARBON MONOXIDE AND HYDROGEN WITH THE INCIDENTAL PRODUCTION OF FREE CARBON, THE IMPROVEMENT WHICH COMPRISES CONDUCTING THE RESULTING PRODUCTS OF REACTION AT SUBSTANTIALLY REACTION TEMPERATURE INTO A FLUIDIZED DENSE PHASE MASS OF SOLID PARTICLES OF REFRACTORY MAINTAINED AT A TEMPERATURE IN THE RANGE OF 500 TO 1000*F. EFFECTING RAPID COOLING OF SAID REACTIONS PRODUCTS WITH SIMULTANEOUS DEPOSITION OF FREE CARBON IN SAID FUIDIZED MASS, DISCHARGING COOLED GASEOUS PRODUCTS OF REACTION SUBSTANTIALLY FREE OF CARBON FROM SAID FLUIDIZED MASS, WITHDRAWING SOLID PARTICLES OF REFACTORY CONTAINING ENTRAPPED CARBON FROM SAID FLUIDIZED MASS, AND INTRODUCING REFRACTORY PARTICLES SUBSTANTIALLY FREE FROM CARBON TO SAID FLUIDIZED MASS TO REPLACE SAID PARTICLES WITHDRAWN THEREFROM. 